Patent GB-963426-A (GB)
Title: Improvements relating to metal-containing formazane reactive dyestuffs and their use
IPC: C09B62/018
Filed: 1961-01-13
Abstract: The invention comprises dyes of formula <FORM:0963426/C4-C5/1> where R1 is a monovalent radicle, A and B are diazo component residues, X is a metal complexing group o to the azo link, Y is an acid dissociating, salt forming, water solubilizing group, W is a m- or p-benzoyleneamido group, R2 is H or an alkyl group of 1 to 4 C atoms, Z is an acyl radicle which has at least one mobile halogen atom, of atomic number 17 to 35, which reacts with alkali whilst splitting off as an anion, or is a substituent containing such an amido group, Me is a metal of atomic number 24 to 29, n is 1 to 5 and q and m are 1 or 2.  The dyes are made in conventional fashion by acylating dyes of the above formula in which Z is H, by metallizing appropriate metal-free dyes or by metallizing a compound of formula <FORM:0963426/C4-C5/2> and coupling the product with an appropriate diazo component. Nickel, cobalt, chromium and copper are specified metals the last named being preferred.  Preferably, A and B are diazo components of the benzene or naphthalene series and R1 is also of these series.  Cyclic carbimide halides, e.g. 2,4,6 - trichloro - 1,3,5 - triazine, 2-alkoxy, -alkyl, -phenyl, -amino, -alkylamino, -phenylamino, -sulphophenylamino, ureido or quanidino - 4,6 - dichloro - 1,3,5 - triazines, 4,6-dibromo-pyrimidines which contain halogen atoms or negative groups, e.g. nitro, acyl and cyano groups in the remaining positions, tetrameric cyanogen chloride,b -halogen alkanoyl and alkenoyl halides, e.g. b -chlorocrotonic bromide, and m - (b  - bromoethylsulphamyl) - benzoyl chloride are indicated as compounds from which Z is derived.  The formazone starting materials are obtained by conventional methods, e.g. by coupling 2 mols. of aryl diazonium compound with 1 mol. of a compound which may be coupled twice at a methylene or methine group, possibly whilst splitting off substituents, or via the hydrazones described in the parent Specification. Diazo components indicated are o-hydroxy- and -carboxy-aminobenzenes and -naphthyl-amines.  They may be substituted by halogen, cyano, nitro, alkyl, amethyl, cycloalkyl, aryl, alkoxy, aryloxy, sulphonic acid, carboxylic acid, carboxylic acid ester, sulphonic acid ester, sulphonic acid alkylsulphonic acid aralkyl- or sulphonic acid aryl-amide, alkyl-carbonyl, aryl carbonyl, alkylsulphonyl, aryl-sulphonyl, alkylamino, aralkylamino, cycloalkylamino, arylamino, stilbylazo, arylazo, acylamino groups or a group of formula <FORM:0963426/C4-C5/3> Ether, acyloxy or desulphonylamide groups may be present in the diazo components in place of the o-hydroxy or o-carboxy groups. Illustrative of indicated non-metallizable diazo components are aminobenzenes, naphthylamines and aminoazoles, e.g. 2-aminothiazoles and -triazoles, 4-aminopyrazoles, 3-amino-indazoles, 4-aminopyridines and 3-aminoquinolines.  If the group <FORM:0963426/C4-C5/4> is in a non-metallizable diazo component it is advantageously a m- or p-monoacylamino-benzene diazonium compound and especially a m- or p-monoacyl or monoazinyl-amino-diazo-benzene-o-sulphonic acid.  As in the parent Specification a -carbonylalkanes, a -acyl- and -cyano-acetic acid esters and a -acylacetic acid arylamides are used as coupling components which couple twice at a methylene or methine carbon atom.  Generally, aromatic-isocyclic aldehydes are used for hydrazone formation, e.g. benzaldehyde, tolualdehydes, 3-nitrobenzaldehyde, anisaldehyde, vanillin, 4-diethyl-aminobenzaldehyde, 4 - dihydroxy - ethyl-aminobenzaldehyde and furfurol, peperorial, pyridine and benzimidazole aldehydes and aliphatic or araliphatic aldehydes, e.g. acetaldehyde, crotonaldehyde and cinnamaldehyde. The intermediates of formula <FORM:0963426/C4-C5/5> aryldiazonium compound with an appropriate methylene or methine compound containing the COOH group, or a group convertible thereto, e.g. a cyanic or carboxylic ester group.  The dyes colour natural and regenerated cellulose fibres in red-brown, violet, blue, green and grey shades.  The dyeings are fixed with acid-binding agents.  Natural and synthetic polyamides may be dyed in an acid bath, or printed with neutral to weakly acid inks, and subsequently treated with acid binding agents. The acid binding agents may be in the impregnating liquors or printing pastes. Numerous examples are given of the preparation of the dyes and their use in colouring cotton and wool.